Dyeings



Patented Feb; 20, 1940 UNITED STATES ramas sumac Petersen,

Le'verkusen-I. G. Werk,

Bayer, and Carl Tanbe. Germany, assignors to General Aniline & Film Corporation, a corporation 0! Delaware No Drawing. Application May 20, 1937, Serial No. 143,726. In Germany May 30, 1938 9 Claims.

The present invention relates to a process oiimproving dyeings on textile fibers and similar material. l

It is known that in many cases dyeings' of organic dyestuffs, especially such as contain tree carboxylic or sulionic acid groups, can be improved by causing the said dyestuffs to interact on the dyed material with organic bases like amines, quaternary ammonium compounds or 10 soluble salts thereof. By such processes the dyestufls are more solidly fixed on the dyed material so that the dyeings will'be of better fastness to water, to washing and the like. The

said treatment has been carried out either by aitertreating the dyedmaterial or by pretreating the material and thereafter. dyeing it with direct or acid dyestuffs. I

We have now round that still. better results are obtained by employing for .the said purpose 2 such organic bases as have combined therewith a metal incomplex form but as are still capable of forming salts with acids. By our new process, for instance, in many cases the fastness o! the dyeings to water will be materially increased whilst in these and other cases the treated dyeings will be much faster to the action of light. Moreover, often a remarkable change 'in color oi the treated dyeing has been observed thus yielding for instance a deeper shade or a'more so valuable tint of increased iastness. The process of our invention has proved to be especially suitable for improving dyeings of substantive. dyestufls on cellulosic textile fibers like cotton or artificial silk from regenerated cellulose. These and other objects and results of our invention will be more fully illustrated by the to]- lowing description thereof.

The metal complex compounds to be used according to our invention are derived from or- 40 ganic bases which may belong to the aliphatic or cyclic series. As examples we may mention the metal complex compounds of guanidino guanidine, oi thiourea, of c-phenanthroline, of phenylene diamines, or -2.2'-dipyridyl, of 8- amino-quinoline, oi 8-amino-quinaldine and the like. The metals suitable for preparing the compounds to be used according to our invention are of the type which easily forms complex compounds with organic bases, for instance, chromium, iron and especially copper.

The process oi our invention may be carried out by ai'tertreating the dyed fibers withan aqueous solution oi one of the said complex metal compounds; if desired, the solution may '55 be weakly acid or alkaline. In another modification of our" process forming of the metal complex compound and attertreating oi the dyeing is per- The aqueous solution 01 the copper vcomplex oi the compound of the following constitution:

is used for the aftertreatment of. a 2% dyeing with Diamine Pure Blue FF (comp. Col. Ind. -No. 517). On aitertreating for half an hour, which aitertreatment can also be effected in an acetic acid or an alkaline solution, there is obtained in contrast to the non-aftertreated 'solution an essentially greener shade. The aftertreated dyeing is distinguished by its fastness to washing and light.

A similarly improved fastness to waterfiand washing is obtained on aftertreating in the usual manner dyeings with Congo Red (Co. Ind. No. 370) or with Direct Deep Black EW.

The above mentioned compound is obtainable by reacting upon 1 mol of cyanuric chloride with 1 mol of m-amino-phenyl-trimethyl am- 'moniumchloride and 1 mol of 5-amino-8-hydroxy-quinoline.

Example 2 A 2% dyeing on cotton with the dyestufi which is obtained by coupling in an alkaline medium diazobenzene and diazotized 2-naphthylamine-6- sulionic acid with the urea of I-acid, is treated, after washing, for half an hour at 30 C. with an aqueous solution of the complex compound pre.. pared from cupric sulfate and. B-amino-quinaldine (obtainable by stirring an alcoholic solution or B-amino-quinaldine into an aqueous cupric sulfate solution). By this treatment the scarlet red dyeing becomes dark brown and acquires a good fastness to washing.

' On treating dyeings of Diamine Green B (comp. Col. Ind. 1st edition, No. 593) in the manner described in the preceding paragraph, these dyeings become essentially faster to washing and deeper.

Example 3 A 2% dyeing oi Diamine Pure Blue FF is dull and faster to washing.

Example 4 Cotton which has been dyed with 7% of Sirius Black L (comp. Schultz, Farbstofltabellen, Erganzungsband, 1934, page 132) is treated in an aqueous. solution at 30 C.- prepared from o-phenanthroline-cupric-chloride (obtainable from ophenanthroline and cupric chloride). The dyeing becomes more greenish and is improved as regards its iastness to washing.

Instead of the copper complex compound of ophenanthroline there can be used the copper.

complex compound of nitro-o-phenanthroline,

. which is obtainable by nitration, or of the reduction product thereof, or of the compound obtainable by causing 1 mol of 2.3-diamino-naphthalane, and 2 mols of glycerine to react according to the method of Skraup.

Example 5 The fastness to water and washing of cotton dyeings prepared with Diamine Green B are improved on aftertreating the same with solutions of the complex salts prepared from cupric chloride with 1 or 2 mols of a.u-dipyridyl.

The fastness to washing of the dyeings is also improved by using the corresponding complex iron salts.

Example 6 Cotton dyed with Direct Deep Black EW extra is aftertreated with the solution of the cupric complex salt of NN-tetramethyl-o-phenylene-diamine. Such solutions may, for instance, be obtained by adding'l mol of base and 1 mol of copper acetate in alcohol and dilution with water of this alcoholic solution which, if desired, may have been filtered. The Iastness to water of the aftertreated dyeings is improved.

A similar efiect is obtained, for instance. by the copper complex solution of N-monomethyl-ophenylenediamine.

We claim:

1. In the process of ganic dyestuffs containing free acid groups on textile fibers the modification which comprises causing the dyed fibers to interact with a complex metal compoundof a cyclic base containingv at least two basic nitrogen atoms which metal compound is capable 01' forming salts with acids.

improving dyeings of orplex copper compound of a cyclic base containing at least two basic nitrogen atoms which copper compound is capable of forming salts with acids.

4. In the process of improving dyeings 0! organic dyestuffs containing free acid groups on cellulosic fibers the modification which comprises causing the dyed fibers to interact with a complex copper compound of a cyclic organic base containing at least two basic nitrogen atoms which copper compound is capable of forming salts with acids.

5. In the process of improving dyeings of organic dyestufiscontaining free acid groups on cellulosic textile fibers the modification which comprises treating the dyed fibers with an aqueous solution of a complex copper compound of a N-heterocyclic base containing at least two basic nitrogen atoms which'copper compound is capable of forming salts with acids.

6. In the process of improving dyeings of organic dyestuffs containing free acid groups on cellulosic fibers the modification which comprises treating the dyed fibers with an aqueous solution of a complex-copper compound of 8-amino-quinoline which copper compound is capable of forming salts with acids.

7. ln'the process of improving dyeings of organic dyestuffs containing free acid groups on cellulosic textile fibers the modification which comprises treating the dyed fibers with an aqueous solution of a complex copper compound of 8-amino-quinaldine which copper compound is capable of forming salts with acids. v

8. Ifextile fibers dyed with organic dyestufis containing free acid groups, said dyed fibers 'being combined with a complex metal compound of a cyclic base containing at least two basic nitro-' 

